• Journal of Electrochemical Science and Technology
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• 제4권3호
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• pp.93-101
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• 2013

The electrodeposition of indium onto a copper electrode from an aqueous sulfate solution containing $In^{3+}$ was studied by means of cyclic voltammetry and chronoamperometry. Reduction and oxidation of indium on copper were investigated by using cyclic voltammograms at different negative limiting potentials and at different scan rates in cumulative cycles. Cyclic voltammograms indicated that reduction and oxidation processes of indium could involve various reactions. Chronoamperometry was carried out to analyze the nucleation mechanism of indium in the early stage of indium electrodeposition. The non-dimensional plot of the current transients at different potentials showed that the shape of the plot depended on the applied potential. The nucleation of indium at potential step of -0.6~-0.8 V was close to progressive nucleation limited by diffusion. However the non-dimensional plot of current transients for the indium nucleation showed different behaviors from theoretical curves at the potential step lower than -0.8 V.

• 대한전기학회논문지:전기물성ㆍ응용부문C
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• 제52권4호
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• pp.164-168
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• 2003

The initial stage of copper electrodeposition has been known to be very important role for morphology and physical properties after final growth. The factors affecting the nucleation are electrode, current density, electrolyte and temperature. Current studies has illuminated the initial nucleation of copper electrodeposition in the viewpoint of the surface status of electrode and analyzed using EIS and SEM observation

• 한국세라믹학회지
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• 제41권6호
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• pp.435-438
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• 2004

MOCVD is one of the major deposition techniques for Cu thin films and Ta-Si-N is one of promising barrier metal candidates for Cu with high thermal stability. Effects of hydrogen plasma pretreatment of the underlying Ta-Si-N film surface on the Cu nucleation in Cu MOCVD were investigated using scanning electron microscopy, X-ray photoelectron spectroscopy and Auger electron emission spectrometry analyses. Cu nucleation in MOCVD is enhanced as the rf-power and the plasma exposure time are increased in the hydrogen plasma pretreatment. The optimal plasma treatment process condition is the rf-power of 40 Wand the plasma exposure time of 2 min. The hydrogen gas flow rate in the hydrogen plasma pretreatment process does not affect Cu nucleation much. The mechanism through which Cu nucleation is enhanced by the hydrogen plasma pretreatment of the Ta-Si-N film surface is that the nitrogen and oxygen atoms at the Ta-Si-N film surface are effectively removed by the plasma treatment. Consequently the chemical composition was changed from Ta-Si-N(O) into Ta-Si at the Ta-Si-N film surface, which is favorable for Cu nucleation.

• 소성∙가공
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• 제22권8호
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• pp.450-455
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• 2013

In the current study, a new dynamic recrystallization model for predicting high temperature flow stress is developed based on a physical model and the mean field theory. In the model, the grain aggregate is assumed as a representative volume element to describe dynamic recrystallization. The flow stress and microstructure during dynamic recrystallization were calculated using three sub-models for work hardening, for nucleation and for growth. In the case of work hardening, a single parameter dislocation density model was used to calculate change of dislocation density and stress in the grains. For modeling nucleation, the nucleation criterion developed was based on the grain boundary bulge mechanism and a constant nucleation rate was assumed. Conventional rate theory was used for describing growth. The flow stress behavior of pure copper was investigated using the model and compared with experimental findings. Simulated results by cellular automata were used for validating the model.

• 한국재료학회지
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• 제11권9호
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• pp.802-809
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• 2001

Electroplating is an attractive alternative deposition method for copper with the need for a conformal and conductive seed layer In addition, the Cu seed layer should be highly pure so as not to compromise the effective resistivity of the filled copper interconnect structure. This seed layer requires low electrical resistivity, low levels of impurities, smooth interface, good adhesion to the barrier metal and low thickness concurrent with coherence for ensuring void-free fill. The electrical conductivity of the surface plays an important role in formation of initial Cu nuclei, Cu nucleation is much easier on the substrate with higher electrical conductivities. It is also known that the nucleation processes of Cu are very sensitive to surface condition. In this study, copper seed layers deposited by magnetron sputtering onto a tantalum nitride barrier layer were used for electroplating copper in the forward pulsed mode. Prior to electroplating a copper film, the Cu seed layer was cleaned by plasma H$_2$ and $N_2$. In the plasma treatment exposure tome was varied from 1 to 20 min and plasma power from 20 to 140W. Effects of plasma pretreatment to Cu seed/Tantalum nitride (TaN)/borophosphosilicate glass (BPSG) samples on electroplating of copper (Cu) films were investigated.

• 대한전자공학회논문지SD
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• 제37권3호
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• pp.27-33
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• 2000

선택성을 향상시키기 위해서 BPSG(Borophosphosilicate glass) 위에 형성한 TiN 패턴을 로(furnace) 열처리와 질소 플라즈마 처리를 한 후 유기 화학 기상 증착법(MOCVD； Metal Organic Chemical Vapor Deposition)으로 구리 박막을 증착하였다. 먼저 650℃∼750℃에서 열처리한 후 150℃에서 구리 박막을 증착시켰을 때 750℃에서 열처리한 경우 TiN 표면 위에만 선택적으로 구리 증착이 일어났다. 질소 플라즈마 처리를 한 경우도 마찬가지로 BPSG 위에 구리 핵 형성이 억제됨을 알 수 있었다. 플라즈마 처리 온도를 증가시킬수록 BPSG 위의 구리 핵 형성이 더 효과적으로 억제되었다. 열처리와 플라즈마 처리 후 증착된 기판 표면을 TOF-SIMS(Time-of-Flight Secondary Ion Mass Spectrometry)로 분석하였을 때 플라즈마 처리가 BPSG 표면의 구리 증착 작용기인 0-H(hydroxyl)기를 제거하여 구리의 선택성이 향상되었다고 해석하였다.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 1999년도 춘계학술발표회 초록집
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• pp.95-96
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• 1999

• 한국재료학회지
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• 제30권4호
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• pp.160-168
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• 2020

The current density in copper electroplating is directly related with the productivity; then, to increase the productivity, an increase in current density is required. This study is based on an analysis of changes in surface characteristics and mechanical properties by applying the addition of Alcian Blue (AB, C₅₆H₆₈Cl₄CuN₁₆S₄). The amount of Alcian Blue in the electrolytes is changed from 0 to 100 ppm. When Alcian Blue is added at 20 ppm, a seed layer is formed homogeneously on the surface at the initial stage of nucleation. However, crystals electroplated in electrolytes with more than 40 ppm of Alcian Blue are observed to have growth in the vertical direction on the surface and the shapes are like pyramids. This tendency of initial nucleation formation causes protrusions when the thickness of copper foil is 12 ㎛. Thereafter, a lot of extrusions are observed on the group of 100 ppm Alcian Blue. Tensile strength of groups with added Alcian Blue increased by more than 140% compare to no-addition group, but elongation is reduced. These results are due to the decrease of crystal size and changes of prior crystal growth plane from (111) and (200) to (220) due to Alcian Blue.

• Journal of Electrochemical Science and Technology
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• 제9권3호
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• pp.202-211
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• 2018

In this work, Fe-Pd alloy films have been electrodeposited on different substrates using an electrolyte containing $[Pd(NH_3)_4]^{2+}$ (0.02 M) and $[Fe-Citrate]^{2+}$ (0.2 M). The influences of substrate and overpotential on chemical composition, nucleation and growth kinetics as well as the electrodeposited films morphology have been investigated using energy dispersive X-ray spectroscopy (EDS), current-time transients, scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) patterns. In all substrates - brass, copper and sputtered fluorine doped tin oxide on glass (FTO/glass) - Fe content of the electrodeposited alloys increases by increasing the overpotential. Also the cathodic current efficiency is low due to high rate of $H_2$ co-reduction. Regarding the chronoamperometry current-time transients, it has been demonstrated that the nucleation mechanism is instantaneous with a typical three dimensional (3D) diffusion-controlled growth in the case of brass and copper substrates; while for FTO, the growth mode changes to 3D progressive. At a constant overpotential, the calculated number of active nucleation sites for metallic substrates is much higher than that of FTO/glass; however by increasing the overpotential, the number of active nucleation sites increases. The SEM micrographs as well as the XRD patterns reveal the formation of Fe-Pd alloy thin films with nanostructure arrangement and ultra-fine grains.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2009년도 제38회 동계학술대회 초록집
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• pp.249-249
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• 2010

The effect of forming a passivation layer was investigated in superconformal Cu gap-filling of the nano-scale trench with atomic-layer deposited (ALD)-Ru glue layer. It was discovered that the nucleation and growth of Cu during metal-organic chemical vapor deposition (MOCVD) were affected by hydrogen plasma treatments. Specifically, as the plasma pretreatment time increased, Cu nucleation was suppressed proportionally. XPS and Thermal Desorption Spectroscopy indicated that hydrogen atoms passivate the Ru surface, which leads to suppression of Cu nucleation owing to prevention of adsorption of Cu precursor molecules. For gap-fill property, sub 60-nm ALD Ru trenches without the plasma pretreatment was blocked by overgrown Cu after the Cu deposition. With the plasma pretreatment, superconformal gap filling of the nano-scale trenches was achieved due to the suppression of Cu nucleation near the entrances of the trenches. Even the plasma pretreatment with bottom bias leads to the superconformal gap-filling.